Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/18—Polybenzimidazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/16—Halogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

• the invention relates to a method for obtaining a composition in the form of a crumb comprising an aromatic polyamide from an aromatic diamine and an aromatic diacid chloride, which aromatic polyamide comprises 5(6)-amino-2-(p-aminophenyl) benzimidazole terephthalamide units and has a relative viscosity ⁇ rel of at least 3 by copolymerizing 5(6) -amino-2-(p-aminophenyl)benzimidazole (DAPBI) and optionally para-phenylenediamine (PPD), and terephthaloyl dichloride (TDC) in a mixture of N-methyl pyrrolidone (NMP) and calcium chloride.
• DAPBI 5(6) -amino-2-(p-aminophenyl)benzimidazole
• PPD para-phenylenediamine
• TDC terephthaloyl dichloride
• a method of adding calcium chloride to a solvent in a polymerization mixture or after the start of the polymerization process is known from U.S. Pat. No. 4,172,938.
• This reference discloses in example 34 the polymerization of a PPD/DABPI/TDC mixture.
• all of the calcium chloride was added in the NMP solvent prior to adding the monomers. Further a low DABPI content (10 mole %) polymer was made. This process did not lead to the forming of a crumb, but only a paste-like product was obtained.
• a method for performing such polymerization reaction but obtaining a composition in the form of a crumb or a crumb-like material was disclosed in WO 2005/054337.
• the monomer of interest DAPBI (5(6)-amino-2-(p-aminophenyl)-benzimidazole)
• DAPBI is added to the aromatic diamine mixture with the objective to obtain a suitable polymer solution right after polymerization with e.g. PPD and TDC, which can be directly shaped into fibers or films, whereby DAPBI is seen as a suitable co-monomer to keep the aramid polymer in solution.
• Said method therefore pertains to a method for obtaining an aromatic polyamide comprising 5(6)-amino-2-(p-aminophenyl)benzimidazole terephthalamide units as a crumb with a relative viscosity ⁇ rel of at least 4.
• This method wherein the monomers are added to the final solvent system (CaCl 2 /NMP) is very suitable for obtaining crumbs and crumb-like materials when performed at the scale as indicated in this patent application, i.e. in a small reaction flask of 2 L.
• the invention pertains now to a method for obtaining an aromatic polyamide crumb from an aromatic diamine and an aromatic diacid chloride, which aromatic polyamide comprises 5(6)-amino-2-(p-aminophenyl)benzimidazole terephthalamide units and has a relative viscosity ⁇ rel of at least 3, by
• the thus obtained crumb material after coagulation and washing with water followed by optionally drying is suitable for making a spin dope by dissolving it in a solvent, for instance sulfuric acid, NMP, NMP/CaCl 2 , N-methyl acetamide, and the like.
• a solvent for instance sulfuric acid, NMP, NMP/CaCl 2 , N-methyl acetamide, and the like.
• the dope can be used to manufacture formed articles, such as fibers, films, and the like.
• crumb or crumb-like as used in this invention means that the polymer in the mixture after polymerization is fully or substantially fully in the form of breakable clumps or particles, which are not sticky (i.e. do not form a lump around stirrer), and have a mean particle size greater than 100 ⁇ m, usually greater than 1 mm. See also the definition of crumbs for PPTA aramid in Encyclopedia of Polymer Science and Technology, Vol. 3, page 565 (John Wiley & Sons) wherein PPTA crumbs are defined as particles with the consistency of wet sawdust.
• the CaCl 2 /aromatic diamine molar ratio in the homogeneous mixture is 0.6-1.0, preferably 0.70-0.80.
• the amount of calcium chloride reaches the claimed molar ratio after the monomers have been homogenized in the solvent.
• small amounts of calcium chloride may be added prior to or during mixing the monomers before being homogenized, for instance one or more of the monomers can be added to the solvent NMP (N-methyl pyrrolidone) and calcium chloride, as long as the molar ratio CaCl 2 /aromatic diamine is less than 0.5, i.e. between 0 and 0.5.
• the remainder of the calcium chloride to obtain a ratio between 0.6 and 1.0 is then added after the monomers have been homogenized in the solvent, preferably as a mixture of calcium chloride and NMP.
• no calcium chloride is present in the solvent to dissolve the monomers and the calcium chloride is only added to the homogeneous mixture, preferably as NMP/CaCl 2 mixture.
• This method of adding calcium chloride is quite unusual because the NMP/CaCl 2 mixture is the solvent (i.e. CaCl 2 adds to the dissolving power of NMP) and an activator for the polymerization reaction. There is no obvious reason or expectation that the reaction would render a different product if the calcium chloride is added in a later phase of the process, i.e. that it renders a crumb whereas no crumb is formed when the calcium chloride is immediately added at the start of the polymerization reaction.
• embodiments of the invention are first mixing the aromatic diamines including DABPI in N-methyl pyrrolidone to a CaCl 2 /aromatic diamine molar ratio of 0, for 1 to 180 min, preferably for 3-30 min, after which TDC is added and mixed for another 1 to 180 min, preferably for 3-30 min, followed by adding calcium chloride to obtain a CaCl 2 /aromatic diamine molar ratio 0.6-1.0.
• the monomer concentration in the solvent should be 5 to 12 wt % in order to obtain crumbs.
• the optimum concentration depends on the DABPI content of the monomer mixture, but can easily be determined by the artisan. As a rule of thumb, the higher the DABPI content, the lower the monomer concentration in the solvent.
• the aromatic diamines include DABPI.
• PPD para-chlorophenylene-diamine
• Me-PPD para-methylphenylenediamine
• the aromatic diacid chloride include TDC, but small amounts (up to 1.2 mole %) of other aromatic diacid chlorides may be present.
• mole % relates to the molar percentage of the monomers with regard to the total of aromatic diamine and aromatic diacid chloride monomers.
• homogeneous mixture and “homogenized” mean that the monomers are homogeneously distributed in the solvent as a solution, emulsion, or suspension.
• Calcium chloride can be added as such or as a mixture, dispersion or solution, such as in the form of an NMP/CaCl 2 mixture.
• the method is particularly suitable for commercial large scale production of polymer as a crumb.
• Said large scale processes are usually performed in reactors of a capacity of at least 50 L, usually much bigger, for instance in reactors of 2500 L to 10.000 L, such as disclosed in EP 0743964.
• the method is particularly suitable for use in a cylindrical reactor having a measure capacity of at least 50 L which is equipped with a single mixing gear used as stirrer and granulator, such as is the case for the Turbulent-Schnellmischer mit viagelmischwerk of Drais.
• the method can also be used in a continuous process.
• Standard Teijin Aramid (Twaron®) polymerization methods for making a copolymer with 20-50 mole % DAPBI containing an overall copolymer composition of 50 mole % TDC, 15-35 mole % PPD and 35-15 mole % DAPBI.
• reaction product was coagulated, washed with demineralized water and dried in a fluid bed dryer (at 150° C.).
• the relative viscosity is defined as the viscosity ratio of a 0.25 wt % polyaramid solution in 96% H 2 SO 4 to the polymer-free solvent (96% H 2 SO 4 ). This ratio is determined with a capillary viscometer (Ubelohde) at 25° C.
• NMP and the amines were mixed in a horizontal cylindrical paddle mixer of Drais having a measure capacity of 160 liter for 30 min and the mixture was cooled to a temperature of 5° C. and TDC was added. After cooling the mixture to 5° C., NMP/CaCl 2 was added to obtain a CaCl 2 /(PPD+DAPBI) molar ratio of 0.72. After one hour of reaction time the reaction product consisting of small crumb-like particles with a relative viscosity of 13.6, was obtained. Polymerization without CaCl 2 in the solvent resulted in PPTA-DAPBI powder with ⁇ rel of maximum 1.2 (comparison; Table 1).
• Polyaramid was prepared according to the method of Example 1, using 25 mole % rather than 35 mole % DAPBI units.
• Table 1 shows that the examples of the invention render crumbs, whereas the prior art method leads to lumps that stuck around the stirrer.
• Polyaramid with 25 mole % DAPBI units was prepared in a ‘Turbulent-Schnellmischer mit viagelmischtechnik’ Drais reactor with a measure capacity of 2500 L.
• NMP/CaCl 2 and the amines (PPD and DAPBI) with a CaCl 2 /(PPD+DAPBI) molar ratio of 0.30 were mixed in a horizontal cylindrical paddle mixer of Drais having a measure capacity of 160 liter for 30 min and the mixture was cooled to a temperature of 5° C. and TDC was added. After cooling the mixture to 5° C., NMP/CaCl 2 was added to obtain a CaCl 2 /(PPD+DAPBI) molar ratio of 0.71. After one hour of reaction time the reaction product consisting of small crumb-like particles with a relative viscosity of 7.1, was obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyamides (AREA)

Applications Claiming Priority (4)

Publications (2)

Family

ID=39512495

Family Applications (1)

Country Status (12)

Cited By (2)

Families Citing this family (20)

Citations (4)

Family Cites Families (2)

• 2009
  • 2009-04-09 CN CN2009801135450A patent/CN102007164B/zh active Active
  • 2009-04-09 DK DK09732969.2T patent/DK2268710T3/da active
  • 2009-04-09 KR KR1020107023192A patent/KR101587791B1/ko active Active
  • 2009-04-09 US US12/937,849 patent/US8362192B2/en active Active
  • 2009-04-09 RU RU2010146934/04A patent/RU2488604C2/ru active
  • 2009-04-09 EP EP09732969A patent/EP2268710B1/fr active Active
  • 2009-04-09 WO PCT/EP2009/054277 patent/WO2009127586A1/fr not_active Ceased
  • 2009-04-09 PL PL09732969T patent/PL2268710T3/pl unknown
  • 2009-04-09 BR BRPI0909395A patent/BRPI0909395A2/pt not_active IP Right Cessation
  • 2009-04-09 ES ES09732969T patent/ES2385133T3/es active Active
  • 2009-04-09 JP JP2011504426A patent/JP5590681B2/ja active Active
  • 2009-04-15 TW TW098112429A patent/TW201002757A/zh unknown

Patent Citations (6)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events